Alkene metathesis is a superb methodology. We report the progress using alkene metathesis in the synthesis of polymeric organic semiconductors. Three classes of polymers have been synthesized using acyclic diene metathesis (ADMET) or ring opening metathesis polymerization (ROMP), viz., poly(acetylene)s (PA), poly(arylene‐vinylene)s (PAV), and organometallic polymers. For PAs, ROMP of cyclooctatetraenes is best, whereas for PAV, both ADMET and indirect and direct ROMP are viable. Metathesis performs flawlessly with the correct monomers, as molybdenum and particularly the robust Ru carbenes demonstrate. When performing ROMP, one is often rewarded with structurally uniform polymers that can display very low polydispersities. Overall, metathesis is a powerful tool for the preparation of semiconducting polymers. 相似文献
Water‐soluble and amphiphilic polymers are of great interest to industry and academia, as they can be used in applications such as biomaterials and drug delivery. Whilst ring‐opening metathesis polymerization (ROMP) is a fast and functional group tolerant methodology for the synthesis of a wide range of polymers, its full potential for the synthesis of water‐soluble polymers has yet to be realized. To address this, we report a general strategy for the synthesis of block copolymers in aqueous milieu using a commercially available ROMP catalyst and a macroinitiator approach. This allows for excellent control in the preparation of block copolymers in water. If the second monomer is chosen such that it forms a water‐insoluble polymer, polymerization‐induced self‐assembly (PISA) occurs and a variety of self‐assembled nano‐object morphologies can be accessed. 相似文献
The ring-opening metathesis polymerization (ROMP) reaction is extraordinarily useful for the preparation of a large variety of polymers. We report that the length (n = 25-50) of high-substituent-density oligopeptide polymers synthesized by ROMP is dramatically improved upon addition of LiCl to reduce polymer and oligopeptide aggregation. This methodology should significantly expand the variety of polymers that may be prepared by ROMP and be of general use with norbornyl oligopeptides of any sequence. 相似文献
A recently developed catalytic living ring opening metathesis polymerisation (ROMP) was investigated using a series of reversible chain transfer agents (CTA) carrying either cyclopentene or cyclohexene rings, differing only in ring strain. All cyclopentene derivatives examined showed significantly faster reaction rates than the corresponding cyclohexene derivatives. This resulted in lower molecular weight dispersities and better control of the molecular weight for the cyclopentene compared to the cyclohexene CTAs. Both Grubbs’ second and third generation catalysts could be employed in catalytic living ROMP using cyclopentene CTA derivatives. The kinetics of different CTAs were studied, block copolymers were synthesised and residual ruthenium quantified by ICP‐OES. All polymers were fully characterised by NMR, GPC and MALDI‐ToF mass spectrometry. The new cyclopentene CTAs are readily synthesised in a few straightforward steps and provide faster reaction kinetics than all previously reported reversible CTAs. 相似文献
Graft-through ring-opening metathesis polymerization (ROMP) using ruthenium N-heterocyclic carbene catalysts has enabled the synthesis of bottle-brush polymers with unprecedented ease and control. Here we report the first bivalent-brush polymers; these materials were prepared by graft-through ROMP of drug-loaded polyethylene-glycol (PEG) based macromonomers (MMs). Anticancer drugs doxorubicin (DOX) and camptothecin (CT) were attached to a norbornene-alkyne-PEG MM via a photocleavable linker. ROMP of either or both drug-loaded MMs generated brush homo- and co-polymers with low polydispersities and defined molecular weights. Release of free DOX and CT from these materials was initiated by exposure to 365 nm light. All of the CT and DOX polymers were at least 10-fold more toxic to human cancer cells after photoinitiated drug release while a copolymer carrying both CT and DOX displayed 30-fold increased toxicity upon irradiation. Graft-through ROMP of drug-loaded macromonomers provides a general method for the systematic study of structure-function relationships for stimuli-responsive polymers in biological systems. 相似文献
We report a general method for the solid-phase synthesis of polymers via the ring-opening metathesis polymerization (ROMP). The method involves polymerization in solution to form a block copolymer, immobilization of the polymer via reaction of one block with a resin-bound functional group, modification of the other block, and liberation of the polymer from the resin. We demonstrated the utility of this approach by generating a block copolymer with an N-hydroxysuccinimidyl ester-substituted block (for on-resin functionalization) and a maleimide-substituted block (for conjugation to the resin). We showed that the Diels-Alder reaction can be employed to immobilize the polymers and that amines of diverse structure can be used to modify the resin-bound polymers. The reversibility of the furan-maleimide Diels-Alder adduct was exploited to liberate the polymer from the support. Specifically, treatment of the resin with cyclopentadiene resulted in complete polymer release. The resulting polymers are functional: they were as potent in assays with the lectin concanavalin A as polymers generated by traditional solution routes. We anticipate that this method can be used for the rapid synthesis of diverse polymers via ROMP. 相似文献
Three of the four possible structures for polymers formed from an achiral monomer through a single ROMP polymerization step have been prepared for a small collection of monomers. Trans,syndiotactic structures have been prepared through chain end control, cis,isotactic polymers have been prepared through enantiomorphic site control, and cis,syndiotactic polymers have been prepared through stereogenic metal control. Stereogenic metal control at the metal center as a means of forming syndiotactic polymers is virtually unknown. Synthesis of ROMP polymers with a regular structure that contain alternating enantiomers from a racemic mixture of monomers is a natural consequence of stereogenic metal control. Ruthenium catalysts do not display ROMP specificities analogous to those described here, perhaps since alkylidene isomers have not been observed for Ru catalysts and the barrier to rotation of the carbene in a generic NHC dichloride Ru catalyst has been calculated to be relatively low. 相似文献
A facile synthesis of oligo(thiophene)-modified (coated) "soluble" star (ball)-shaped polymers has been achieved via sequential living ring-opening metathesis polymerization (ROMP) of norbornene and a cross-linking reagent using Mo(CHCMe(2)Ph)(N-2,6-(i)Pr(2)C(6)H(3))(O(t)Bu)(2) as the initiator and oligo(thiophene) carboxaldehydes for termination. The resultant star-shaped ROMP polymers containing ter- and tetrathiophene moieties exhibit unique emission properties due to an integration of the ROMP polymers (arranged functionalities): the blue emission was tuned to the white emission upon addition of 2-[2-[(E)-4-(dimethylamino)styryl]-6-methyl-4H-pyran-4-ylidene]malononitrile. 相似文献
Polymers having α,β‐unsaturated anhydrides as repeating units were synthesized by ring opening metathesis polymerization (ROMP). The anhydride moieties were ready‐to‐be‐grafted with amines to form acid‐labile cis‐α,β‐unsaturated acid amide linkages. The pH‐responsive reversible de‐grafting can be controlled by changing the intramolecular accessibility between acid and amide groups. The alendronate‐grafted ROMP polymers showed distinct pH‐dependent cytotoxicity according to the anhydride structures. 相似文献
Controlled preparation of brush polymers is important in the design of functional materials. In this study, poly(tert-butyl acrylate) macromonomers functionalized with norbornenyl end group(NB-PtBA) were synthesized via atom transfer radical polymerization in three different molecular weights, 2000(NB-PtBA-2k), 3000(NB-PtBA-3k), and 8000(NB-PtBA-8k). Additionally, brush polymers with PtBA as side chains were synthesized via ring-opening metathesis polymerization(ROMP). Kinetic studies on ROMP of NB-PtBA showed that there was a ceiling degree of polymerization(CDP) for the brush polymers, beyond which the polymerization of NB-PtBA was out of control. For brush polymers of P[NB-PtBA-2k] and P[NB-PtBA-3k], CDPs were estimated to be ca. 400, but the value of P[NB-PtBA-8k] was ca. 100. Therefore, the controlled ROMP of brush polymers was critical at the CDP limit with increased macromonomer molecular weight. 相似文献
The use of molecularly imprinted polymers (MIPs) prepared by ring-opening metathesis polymerization (ROMP) for bisphenol A
(BPA) was reported in this article. The resulting MIPs have high imprinting and adsorption capacities, and can be used for
separation and determination of BPA in environmental water samples. The successful application of ROMP in the molecular imprinting
field is described here. For the first time, two cross-linkers (dicyclopentadiene and 2,5-norbornadiene) and two Grubbs catalysts
(first and second generation) were investigated to compare their effects on the binding performance of MIPs. The ROMP technique
is able to create the imprinted polymers within 1 h under mild conditions. Furthermore, it can provide MIPs with obvious imprinting
effects towards the template, very fast template rebinding kinetics, high binding capacity and appreciable selectivity over
structurally related compounds. The adsorption process for MIPs in this study can be completed within 45 min, which is much
faster than that of bulk MIPs synthesized by traditional free-radical polymerization. The resulting imprinting polymer was
evaluated for its use as a sorbent support in an off-line solid-phase extraction approach to recover BPA from diluted aqueous
samples. The optimized extraction protocol resulted in a reliable MISPE method suitable for selective extraction and preconcentration
of BPA from tap water, human urine and liquid milk samples. This article demonstrates the practical feasibility of the MIPs
prepared via ROMP as solid-phase extraction materials. 相似文献
The synthesis of thiol‐functionalized long‐chain highly branched polymers (LCHBPs) has been accomplished in combination of ring‐opening metathesis polymerization (ROMP) and thiol‐Michael addition click reaction. A monotelechelic polymer with a terminal acrylate and many pendent thiol groups is first prepared through adding an internal cis‐olefin terminating agent to the reaction mixture immediately after the completion of the living ROMP, and then utilized as an ABn‐type macromonomer in subsequent thiol‐ene reaction between acrylate and thiol, yielding LCHBPs as the reaction time prolonged. Au nanoparticles are then covalently conjugated onto the surface of thiol‐functionalized LCHBP to fabricate novel hybrid nanostructures, which is shown as one interesting application of such functionalized metathesis polymers. This facile approach can be extended toward the fabrication of novel nanomaterials with sophisticated structures and tunable multifunctionalities.
Photo‐redox mediated ring‐opening metathesis polymerization (photo‐ROMP) is an emerging ROMP technique that uses an organic redox mediator and a vinyl ether initiator, in contrast to metal‐based initiators traditionally used in ROMP. The reversibility of the redox‐mediated initiation and propagation steps enable spatiotemporal control over the polymerization. Herein, we explore a simple, inexpensive means of controlling molecular weight, using alpha olefins as chain transfer agents. This method enables access to low molecular weight oligomers, and molecular weights between 1 and 30 kDa can be targeted simply by altering the stoichiometry of the reaction. This method of molecular weight control was then used to synthesize a functionalized norbornene copolymer in a range of molecular weights for specific materials applications. 相似文献
Polynorbornenes substituted with two different peptide sequences from the RGD-containing integrin cell-binding domain of fibronectin are potent inhibitors of human foreskin fibroblast cell adhesion to fibronectin-coated surfaces. Ring-opening metathesis polymerization (ROMP) using Ru==CHPh(Cl)(2)(PCy(3))(DHIMes) (1) as an initiator produced polymers substituted with GRGDS and PHSRN peptide sequences. The inhibitory activity was quantified for these polymers and compared to the free peptides and GRGES-containing controls. A homopolymer substituted with GRGDS peptides was significantly more active than the free GRGDS peptide (IC(50) of 0.18 +/- 0.03 and 1.33 +/- 0.20 mM respectively), and the copolymer containing both GRGDS and PHSRN is the most potent inhibitor (IC(50) of 0.04 +/- 0.01 mM). These results demonstrate that significant enhancements of observed biological activity can be obtained from polymeric materials containing more than one type of multivalent ligand and that ROMP is a useful method to synthesize such well-defined copolymers. 相似文献